Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups

Definitions

• the present invention relates to a novel curing resin. More particularly, the present invention relates to a novel curing resin and a curing resin-com­position thereof which will be cured by irradiation with ultraviolet rays and electron rays and which are useful for printing inks and paint binders in particular.
• a radiation curing resin which will be cured by irradiation with ultraviolet rays and electron rays, etc. has been developed in fields such as printing inks, paints and adhesives because it has the remarkable and advantageous characteristics such as rapid cure pro­perties, energy-saving properties and low public pol­lution properties.
• a curing resin is used by blending a radical polymerization monomer, usually one such as trimethylol­propane triacrylate with a radical polymerization initiator and a pigment, etc. according to necessity.
• the radiation curing resin is an especially important component of printing inks and paints since it has a predominant effect on various properties such as curing speed, viscosity and coating characteristics.
• a multifunctional oligomer, as a radiation curing resin, such as epoxy acrylate, urethane acrylate, alkyd and polyester acrylate is employed.
• a radiation curing resin having all three properties relating to curing properties, coating characteristics and adhesion has not been previously known.
• epoxy acrylate and urethane acrylate have high visco­sities for their molecular weight and the viscosities change greatly according to the temperature because of strong hydrogen bonds. Also, when they are used for printing inks, the dispersibility of pigments is low.
• epoxy acrylate has a high hydrophilic property and, for example, when it is used for printing inks the emulsion property is bad because it has the same number of hydroxy groups as one of acryloxy group in the resin. Polyester acrylate is slow to be cured.
• examples of a component A having the above-mentioned general formula are cyclo­pentadiene and methylcyclopentadiene, etc.
• examples of a component A which is an addition product formed by the Diels-Alder reaction are dicyclopentadiene, cyclo­pentadiene-methylpentadiene-Diels-Alder codimerization products and tricyclopentadiene, etc. From the point of industrial use the mixture thereof is used preferably.
• Especially preferred are cyclopentadiene, dicyclopenta­diene and the mixture thereof.
• High purity cyclopentadiene, dicyclopentadiene or alkyl-substituted derivatives thereof is not always necessary. However, not less than 80 % purity of these compounds is preferred. Also, a condensed fraction is usable obtained by eliminating most of the C5 components such as C5 olefin and C5 paraffin by distillation from the mixture of dicyclopentadiene, dimethylcyclopenta­diene, cyclopentadiene-methylcyclopentadiene codimer, cyclopentadiene-isoprene codimer and cyclopentadiene-­piperylene codimer, etc., which mixture is obtained by heat dimerization of the cyclopentadiene and methyl­cyclopentadiene which are included in the C5 fraction in the by-product oil obtained by high temperature thermal cracking of naphtha, etc.
• component A′ is compounds having 8 to 20 carbon atoms such as styrene, ⁇ -methylstyrene, vinyl­toluene, indene and methylindene or a mixture thereof. From an industrial point of view, for example, the C9 fraction which is produced as a by-product at the time of cracking of naphtha, etc. is preferably used.
• Component B which is a compound having both at least one polymerizable double bond and at least one hydroxy group in the molecule, includes unsaturated compounds having hydroxy groups which are heat-copoly­merizable with component A, preferably having 3 to 22 carbon atoms, which are unsaturated alcohols such as allyl alcohol, methallyl alcohol, crotyl alcohol, cinnamyl alcohol, methyl vinyl carbinol, allyl carbinol and methyl propenyl carbinol, etc.; unsaturated dihydric alcohols such as 2-butene-1,4-diol and 3-hexene-2,5-diol, etc.; hydroxy alkyl acrylate such as 2-hydroxy ethyl acrylate and 2-hydroxy propyl acrylate, etc. and hydroxy methacrylates such as 2-hydroxy propyl methacrylate, etc., and a mixture of more than one of the above com­pounds.
• unsaturated alcohols such as allyl
• the cyclopentadiene resin used in this invention can be prepared by reacting 2 to 120 parts by weight, preferably 5 to 100 parts by weight, of component B with 100 parts by weight of component A under heating at a temperature from 150 to 300°C, preferably 200 to 280°C, for from 10 minutes to 20 hours, preferably from 1 hour to 10 hours, without catalyst.
• the ratio of component B based on component A in the copoly­merization reaction for the preparation for the resin R3 is very important. This is why in the case of less than 2 parts by weight of component B based on 100 parts by weight of component A, curing of the resin is not suf­ficient, and in the case of more than 120 parts by weight of component B, the yield of cyclopentadiene resin having hydroxy groups (R1) becomes much lower and the coating characteristics are worsened very much as well as the fact that the softening point of the resin becomes lower.
• the cyclopentadiene resin (R1) having hydroxy groups obtained in the above way may be reacted, as it is, with component C which is a polyisocyanate compound.
• component C which is a polyisocyanate compound.
• the cyclopentadiene resin (R1) has a strong smell and is quite colored because it has many double bonds. Therefore, the resin (R1′) which is improved in respect to smell and color can be obtained if only the double bonds in the resin (R1) are hydrogenated without decreasing the number of hydroxy groups in the resin (R1).
• the con­dition for hydrogenation of the resin (R1) is necessary to be selected carefully in order to hydrogenate only the carbon-carbon double bonds in the resin without decreas­ing the number of hydroxy groups in the resin.
• the reaction is necessary to be carried at as low a temperature as possible and a temperature of not more than 200°C is preferred. If the reaction temperature exceeds 200°C, the hydroxy group content in the resin (R1′) is apt to decrease because of dehydration reaction occurring at the same time as that of hydrogenation of carbon-carbon double bonds. Therefore, such condition is not preferred.
• the polyisocyanate compound of component C is one having more than one isocyanate group in the mol­ecule.
• Examples are aliphatic polyisocyanate, alicyclic polyisocyanate, heterocyclic polyisocyanate or aromatic polyisocyanate.
• Examples are butylene-1,4-diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-­diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-di­phenylmethane diisocyanate, diphenyl-3,3′-dimethyl-­4,4′-diisocyanate, xylene diisocyanate, 1-methoxy-­phenylene-2,4-diisocyanate, benzene-1,2,4-triisocyanate, tolidene diisocyanate, is
• a mixture of more than one of these isocyanates can be used. Normally, those having 4 to 30 carbon atoms are employed.
• the reaction between the cyclopentadiene resin having hydroxy groups (R1 or R1′) and the polyisocyanate compound which is component C is carried out at the temperature of from 20 to 280°C, preferably from 30 to 260°C, for 10 minutes to 20 hours, preferably 30 minutes to 15 hours.
• the amount of polyisocyanate to be used in the reaction is in the range of from 0.02 to 0.95, preferably from 0.05 to 0.9, of isocyanate group equivalent based on the equivalent of hydroxy groups in the cyclopentadiene resin having hydroxy groups (R1 or R1′).
• the curing resin of the present invention is obtained by esterification of the hydroxy groups in the resin (R2) with the carboxyl group in the ⁇ , ⁇ -­unsaturated carboxylic acid, reacting the resin (R2) obtained in the above-mentioned way with ⁇ , ⁇ -unsaturated carboxylic acid which is component D under the conditions of the usual and conventionally known esterification reaction per se .
• Examples of the ⁇ , ⁇ -unsaturated carboxylic acid, which is component D, which are to be used in the above reaction are compounds having 3 to 20 carbon atoms and carbon-carbon double bond in the ⁇ , ⁇ position of the carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, sorbic acid and cinnamic acid, etc. And, a mixture of more than one of these compounds can be used also.
• the prescribed object of the present invention is achieved by reacting the resin (R2) with the ⁇ , ⁇ -­ unsaturated carboxylic acid at an equivalent ratio of ⁇ , ⁇ -unsaturated carboxylic acid of from 0.1 to 1.1, pre­ferably from 0.5 to 1.1, based on the amount of hydroxy groups in the resin (R2).
• an equivalent ratio of ⁇ , ⁇ -unsaturated carboxylic acid of from 0.1 to 1.1, pre­ferably from 0.5 to 1.1, based on the amount of hydroxy groups in the resin (R2).
• the curing resin of the present invention is most suitable for use for an irradiation curing resin composition.
• the viscosity is adjusted and diluents are compounded in order to adjust the character and curing rate of the curing composition.
• reactive diluents for these diluents, various kinds of known solvents can be used, in particular in order to make the curing rapid and easy it is preferred that reactive diluents which as described below should be used.
• reactive diluents to be used in the present invention one or more than one of a mixture of compounds having reactive double bonds which can effect a crosslinking reaction with the curing resin of the present invention by irradiation using radiation such as ultraviolet rays or electron beams or by heating.
• acrylic acid derivatives or vinyl compounds such as styrene are preferably used, particularly acrylic acid derivatives are the most suitable.
• Examples of these compounds are one functional monomers such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl­(meth)acrylate, allyl(meth)acrylate, butyl(meth)acrylate, amyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)­acrylate, capryl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate, myristyl(meth)acrylate, cetyl­(meth)acrylate, stearyl(meth)acrylate, benzyl(meth)­acrylate, methacrylate of alkylene oxide addition pro­ducts of alkylphenol, such as phenoxyethyl(meth)acrylate, cyclohexyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyloxyalkyl(meth)acrylate
• Examples of more than one functional monomers are crosslinking sol­vents having acrylic or methacrylic residual groups such as ethylene glycol, di(meth)acrylate, diethylene glycol­di(meth)acrylate, triethylene glycoldi(meth)acrylate, polyethylene glycoldi(meth)acrylate, propylene glycol­di(meth)acrylate, dipropylene glycoldi(meth)acrylate, tripropylene glycoldi(meth)acrylate, butylene glycol­di(meth)acrylate, pentyl glycoldi(meth)acrylate, neo­pentyl glycoldi(meth)acrylate, hydroxypivalic acid neo­pentyl glycol ester di(meth)acrylate, butane dioldi­(meth)acrylate, hexane diol(meth)acrylate, (di)glycerol poly(meth)acrylate, (di)glyce
• the amount of dilution solvent to be used is 10 to 95 parts by weight, preferably 20 to 90 parts by weight, based on 90 to 5 weight parts of the curing resin (R3).
• dilution solvents used exceeds 95 parts by weight, there is little effect of using the curing resin (R3) and sufficient curing property is not obtained. If dilution slvents is used in the amount of less than 10 parts by weight, workability is bad because the viscosity is too high and in the case of use for printing ink the dispersibility of pigment becomes worse and the gloss becomes much worse.
• the above curing resin can be suitably used for binder for printing inks and for paints.
• various kinds of pigments, fillers and additives such as heating polymerization inhibitors, leveling agents and wax, etc. can be compounded with the curing resin.
• curing accelerators can be added and in many cases this is preferable.
• organic peroxide independently or with decomposition accelerators is used, or certain kinds of ketone resins can be used as heating curing accelerators.
• sensitizers such as various kinds of benzoin ether and benzophenone, etc. can be used for curing accelerators.
• the above curing composition has an excellent property which makes the curing very rapid by crosslink­ing reaction by heating or radiation irradiation. Also, the cured film has excellent adhesion and high hardness, when it is used for binders for printing inks or paints, particularly excellent properties can be shown.
• This resin (I) (100 g) was dissolved in com­mercially available mixed xylene, palladium having a palladium concentration of 5 % (5 % Pd-C standard grade made by Nippon Engelhard Ltd.) (1 g) was added, a hydro­genation reaction was carried out under a hydrogen pres­sure of 30 kg/cm2 at a temperature of 150°C for about one hour, the solvent was removed and a hydrogenated resin (I′) was obtained.
• the obtained hydrogenated resin (I′) (100 g) was melted under heating of 140°C, 9.3 g of hexamethylene diisocyanate [the isocyanate group equivalent ratio based on the amount of hydroxy in the resin (I′) was 0.3] was added dropwise and the reaction was carried out for three hours under the atmosphere of nitrogen.
• the softening point of the resin (II) was 117°C, its hydroxy content was 0.49 mol/100 g, its bromine number was 78 and its hue (Gardner) was 11.
• the obtained resin (II) (100 g) was melted under heating at 200°C, 30.6 g of diphenylmethane di­isocyanate [the isocyanate group equivalent ratio based on the amount of hydroxy in the resin (II) was 0.5] was added dropwise and the reaction was carried out at a temperature of 200°C for 2 hours under an atmosphere of nitrogen.
• a C5 fraction (boiling point 26°C to 60°C) produced by cracking of naphtha was heated at a tempera­ture of 110°C for 5 hours, the residue remaining after removal of C5 fraction by distillation had 85 % of di­cyclopentadiene (DCPD) and the others in it were codimers of cyclopentadiene and piperylene or isoprene, 155 g of this fraction including 85 % of DCPD, 58 g of allyl alcohol and 70 g of mixed xylene were charged into an autoclave equipped with a stirrer, were reacted under heating of 260°C for 5 hours and 180 g of the resin (III) was obtained by removing unreacted materials, low grade polymers and solvents.
• the softening point of the resin (III) was 85°C, its bromine number was 75, its hydroxy content was 0.36 mol/100 g and its hue (Gardner) was 10.
• the obtained resin (III) was dissolved in 75 g of xylene and hydrogenation reac­tion was carried out in the same manner as in Example 1.
• the obtained resin (III′) had 83°C of softening point, 19 of bromine number, 0.36 mol/100 g of hydroxy content and 3 of hue (Gardner).
• Ink was obtained from the resin (No. 8) in the same way to make inks as in Comparative Example 1.
• SP-1509 Showa Kobunshi, epoxy acrylate pre­polymer
• trimethylolpropane triacrylate carmine 6B
• irgacure 184 and hydroquinone were compounded at rates described in Table 1, and ink was obtained in the same way as in Examples 7 to 12.
• gloss of printed matters after curing obtained above was observed by the naked eye and was evaluated in accordance with below standards.
• the pencil scratching test was carried out according to JIS K-5400.
• the surface of curing paint film was rubbed with gauze wetted with methyl ethyl ketone and the state of the surface was observed by the naked eye. It was evaluated by below standards. ⁇ : No change. No clouding or no scratch on the surface of curing paint film was pro­duced. The gloss did not lower. X : Change was observed. Clouding or scratch on the surface of curing paint film was produced. The gloss lowered.
• the abrasion test of the curing paint film coated on a PMMA board was carried out by rotary abrasion tester (Toyo Seiki Corp.) in accordance with A.S.T.M. D-1044-78 and the extent of abrasion was evaluated by haze values (%) by hazemeter (Suga Shikenki Corp.) Table 1 No.
• the resin produced accord­ing to the present invention has excellent properties for a curing resin and can be employed for wide range of use.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Polyurethanes Or Polyureas (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Paints Or Removers (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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Citations (4)

• 1988
  • 1988-12-14 JP JP63313761A patent/JPH02160821A/ja active Pending
• 1989
  • 1989-12-13 EP EP19890313054 patent/EP0373925A3/fr not_active Withdrawn

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